This application concerns novel organic phosphorus-inorganic phosphorus oxyacid compounds, it""s basic salts and compositions. These compounds contain two or more phosphorus atoms in each molecule. The flame retardant compounds of this invention may be utilized as flame retardants by incorporating these compounds within or coating a more flammable organic material. In particular, it relates to flame retardant compounds and a flame retardant organic resin compositions, which are free from toxicity problems due to halogen gas generated during combustion or molding as in the use of a halogen-containing flame retardant compound.
Basic nitrogen containing salts of organic polyphosphorus compounds were produced by Blount in U.S. Pat. No. 6,054,515 and utilized in flame retardant compositions. The organic phosphorus-inorganic phosphorus oxyacids compounds of this invention are novel. These novel compounds are an improvement over the basic salts of organic polyphosphorus compounds because they are a much better flame retardant compounds and cost less to produce. When the organic phosphorus-inorganic phosphorus oxyacid compound is incorporated in or on a flammable organic material it produces an intumescent composition. When this intumescent composition is exposed to a flame for a few seconds it begins to char and form bubbles within the char thereby protects the substrate against heat and fire damage for an appreciable time. This intumescence also reduces the amount of smoke produced. The organic phosphorus-inorganic phosphorus oxyacid compounds promote initial intumescence at a low temperature, which is much lower that required when a basic nitrogen salt of organic polyphosphorus compound or an organic phosphorus compound is utilized as the flame retardant compound. The flame retardant compounds of this invention will also with stand a higher temperature than the organic phosphorus compounds and basic nitrogen containing salts of organic polyphosphorus compounds before decomposing, and allows them to be mixed in thermoplastic resin to produce flame retardant reins.
The object of this invention is to produce organic phosphorus-inorganic phosphorus oxyacid compounds, its basic salts and compositions containing these compounds which are capable of rendering organic material less flammable. These flame retardant compounds may be used in the production of insulation foam, flexible foams, building components, coating agents, molded plastic products and as hydraulic fluids, lubricants, surfactants, molded plastic products and many other uses.
In one respect, the invention comprises reacting organic phosphorus compounds, containing phosphorus atom with a valence of 3-4, with inorganic phosphorus oxyacid compounds with phosphorus atoms with a valence of 5 to produce organic phosphorus-inorganic phosphorus oxyacid compounds. Another aspect, the invention comprises utilizing the organic phosphorus-inorganic phosphorus oxyacid of this invention by incorporating in, or apply on a more flammable organic material to render the organic material less flammable. Another aspect of the invention is a process to prepare the organic phosphorus-inorganic phosphorus oxyacid compound comprising serially contacting and reacting:
A) an organic phosphorus compound containing a phosphorus atom with a valence of 3-4;
B) an inorganic phosphorus oxyacid compound containing a phosphorus atom with a valence of 5; under conditions sufficient to prepare the organic phosphorus-inorganic phosphorus oxyacid compound.
Another aspect of this invention is to produce a flame retardant composition which comprising mixing and reacting:
A) an organic phosphorus compound containing a phosphorus atom having a valence of 3-4;
B) an inorganic phosphorus oxyacid compound containing a phosphorus atom with a valence of 5;
then add and mix
C) carbonization auxiliaries
D) carbonization accelerating compounds
G) heat reflecting substance
F) filler
under conditions sufficient to prepare the organic phosphorus-inorganic phosphorus oxyacid compound.
In another aspect, according to this invention there is provided a flame retardant basic salt of organic phosphorus-inorganic phosphorus oxyacid compound produced by a process comprising of serially mixing and reacting:
A) organic phosphorus compound containing a phosphorus atom having a valence of 3-4;
B) inorganic phosphorus compound containing a phosphorus atom having a valence of 5; then mix and react;
C) basic salt forming compound thereby producing a basic salt of organic phosphorus-inorganic phosphorus oxyacid;
then add and mix
D) carbonization auxiliaries
E) carbonization accelerating compounds
F) filler
under conditions sufficient to prepare the salt of organic phosphorus-inorganic phosphorus oxyacid.
In another aspect, according to this invention, there is provided a flame retardant thermoplastic resin composition which comprises (1) thermoplastic resin, (2) organic phosphorus-inorganic phosphorus oxyacid, (3) carbonization auxiliaries, (4) metal containing compound having a carbonization accelerating effect, (4) comb-like polymer and (5) filler.
The components may be utilized in any suitable amount but preferably:
1. Organic phosphorus compound, which contains a phosphorus atom containing a valence of 3-4, in the amount of 25 to 100 parts by weight;
2. Inorganic phosphorus oxyacid compound, which contains a phosphorus atom with a valence of 5, in the amount of 10 to 100 parts by weight;
3. An amount of 5% to 30% by weight of the flame retardant compound or it""s basic salt or it""s composition is added to or applied on the flammable organic material;
4. Basic salt forming compound in the amount of 0 to 100 parts by weight;
5. metal containing compound having a carbonization accelerating effect in the amount of 0 to 40 parts by weight;
6. Comb-like polymer, in the amount of 0 to 100 parts by weight
7. Heat reflecting compound, such as titanium oxide, in the amount of 0 to 30 parts by weight.
8. Filler, in the amount of 0 to 400 parts by weight.
9. Carbonization auxiliaries, 0-100 parts by weight.
Any suitable organic phosphorus-compound, that contains a phosphorus atom with a valence of 3-4, may be used in this invention, such as, but not limited to, organic phosphites, phosphonates, phosphate, hydrogen phosphites, hydrogen phosphates, polyphosphates, polyphosphonates, polyphosphites, phosphites-phosphates, phosphorus esters, polyphosphorus esters, acid phosphates, polyphosphonate esters, diphosphonic acid esters, phosphorus esters and phosphines, alkyl chlorophosphines and mixtures thereof. The organic phosphonate are the preferred organic phosphorus compound.
Suitable organic phosphates include alkyl phosphites, dialkyl phosphites, trialkyl phosphites, dialkyl hydrogen phosphite, diaryl phosphites, aryl-alkyl phosphites, triaryl phosphites, dialkyl-aryl phosphites, etc. Suitable organic phosphonates include dialkyl alkyl phosphonates, aryl-alkyl phosphonates, diaryl alkyl phosphonates, etc. Suitable organic phosphates include alkyl dihydrogen phosphates, dialkyl hydrogen phosphates, trialkyl phosphates, aryl dihydrogen phosphates, diaryl hydrogen phosphates, triaryl phosphates, aryl-dialkyl phosphate, diaryl alkyl phosphate, etc. Commercially available organic phosphorus compounds which contain a phosphorus atom with a valence of 3 or 4 such as those produced by xe2x80x9cALBRIGHT and WILSON which include ANTIBLAZE CU, a cyclic phosphonate ester, ANTIBLAZE N, a cyclic phosphonate ester, ANTIBLAZE V225, a mixture of alkyl and aryl phosphate esters, ANTIBLAZE V400, an organo phosphate/phosphonate, ANTIBLAZE V490, an organo phosphonate ester, ANTIBLAZE 1045, a cyclic diphosphate ester, ANTIBLAZE DMHP-HP, dimethyl hydrogen phosphite, ANTIBLAZE TEP-HP, triethyl phosphitexe2x80x9d, and other commercially available organic phosphorus compounds which contains phosphorus atoms with 3-4 valences.
Any suitable inorganic phosphorus oxyacid compound which contains a phosphorus atom with a valence of 5 may be used in this invention. Suitable inorganic phosphorus compounds include, but not limited to, phosphoric acid, polyphosphoric acid, pyrophosphoric acid, phosphorus oxide, salts of hydrogen phosphoric acid, phosphonic acid, ammonium hydrogen phosphate, ammonium polyphosphate, triphosphorus acid, phosphinic oxide, phosphorus esters, phosphorus trioxide, phosphorus pentioxide, metaphosphoric acid, phosphorus acid, hypophosphorus acid, and mixtures thereof. Phosphoric acid is the preferred inorganic phosphorus oxyacid.
An suitable salt forming compound that will react with an organic phosphorus compound or inorganic phosphorus compound may be used in this invention. Suitable salt forming compounds include, but not limited to, compounds containing alkali metals, alkaline earth metals, metals, and nitrogen containing compounds such as compounds containing ammonium radicals, ammonia, amines, amino compounds, polyamines, and aminoplasts, other nitrogen containing compounds and mixtures thereof. Alkylanolamine compounds are the preferred salt forming compounds, particularly ethanolamine. It is not always necessary to use basic salt forming compounds but when used it is utilized in the amount of 5-100 parts by weight.
Any suitable carbonization auxiliaries may be utilized in this invention. Suitable carbonization auxiliaries are compounds that in the presence of fire assist the formation of a carbonization foam or char, such as, additives that produce acidic components in the pyrolysis mixture, such as phosphorus acids, boric acids or sulfuric acids. These acidic components are compounds such, for example, acids or salts, or their derivatives of sulfur, boron and phosphorus, such as, boron-phosphates, phosphates, and polyphosphates of ammonia, amines, polyamines, amino compounds, thioureas and alkyanolamines, but boric acid and its salts and their derivatives, organic phosphorus compounds and their salts, halogenated organic phosphorus compounds, their salts and their derivatives may also be used for this purpose.
Phosphorus containing compounds, such as, boron-phosphates, phosphates, and polyphosphates of ammonia, amines, polyamines, amino compounds, thioureas and alkyanolamines, boric acid and its salts and their derivatives, organic phosphorus compounds and their salts, halogenated organic phosphorus compounds, their salts and their derivatives may also be used for this purpose. The carbonization auxiliaries and other flame retardant agents may be used in quantities of 0 to 100 parts by weight. In many compositions they are not necessary but when used, it is used in the amount of 5 to 100 parts by weight.
The nitrogen containing salts of phosphorus acids are the preferred carbonization compounds, such as amine phosphates, amine salts of organic phosphorus compounds, amino phosphate, amino salts of organic phosphorus compounds and amino condensation salt of inorganic and organic phosphorus compounds. The amino condensation salt of phosphorus compounds are produced by contacting the amino condensation compounds with phosphorus containing compound that will react with an amino compound, under conditions sufficient to prepare an amino condensate salt of a phosphorus containing compound. Suitable inorganic phosphorus compounds include, but not limited to phosphoric acid, pyrophosphoric acid, triphosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, phosphinic acid, phosphinous acid, phosphine oxide, phosphorus trihalides, phosphorus oxyhalides, phosphorus oxide, mono-metal hydrogen phosphates, ammonia dihydrogen phosphate, bromated phosphates, alkaline metal dihydrogen phosphate and halogenated phosphate-phosphite and their halides and acids. Organic phosphorus compounds include, but not limited to, alkyl, cyclic, aryl and alkyl-aryl phosphorus compounds, such as, alkylchlorophosphines, alkyl phosphines, alkyl phosphates, dialkyl hydrogen phosphates, dialkyl alkyl phosphonates, trialkyl phosphates, organic acid phosphates, organic phosphonate esters, aryl phosphates, aryl hydrogen phosphates, halogenated phosphonates esters and mixtures thereof, Amino condensation borates may be produced by contacting boric acid and amino condensation compound under conditions sufficient to prepare the amino condensation borates which may also be utilized and also ammonia borates may be used. Amino condensation boron-phosphates may be produced by contacting boron-phosphates and amino condensation compounds under conditions sufficient to prepare amino condensation boron-phosphate compounds which may also be utilized. The salt forming phosphorus containing compounds will react with the amino condensation compounds to form an amino condensation salt of a phosphorus containing compound which may also be used.
Any suitable filler may be used in this invention. The fillers that may be utilized in the flame retardant mixture are usually insoluble in the reaction mixtures. They may be Inorganic substances, such as, alkali metal silicates, alkaline earth metal silicates, metal silicates, silica, metals, metal oxides, carbonates, sulphates, phosphates and borates, Portland cement, grass beads, or hollow beads. Hydrated aluminum oxide is the preferred inorganic compound. They may be organic substances such as amino compounds, such as urea, melamine, dicyandiamide, and other cyanuric derivatives or their formaldehyde resins, aminophosphates, amino salts of organic phosphates, phenol-aldehyde resin powder, powdered coke, graphite, graphite compounds and mixtures thereof, The organic halide flame retardant compounds may also be added as filler.
Any suitable organic material which is more flammable than the organic phosphorus-inorganic phosphorus oxyacid compounds or their basic salts of this invention may be used in this invention. Any suitable plastic resin composition or mixtures thereof and any suitable natural organic material may be used in this invention and mixtures thereof. These materials may be in the form of a solid, cellular, suspension, emulsion or solution. Suitable plastic resin include, but not limited to, vinyl dienes, vinyl diene copolymers, polyesters, polyester resins, phenoplasts, aminoplasts, polyepoxy resins, polyurethane, furans, polyamides, polyimides, polycabonates, silicones, polyethers, thioplasts, polytetrafluoroethylene, polysulfones, urethane-epoxy resins, urethran silicate resins or foams, cellulose nitrates, regenerated cellulose, cellulose esters, cellulose ethers, cyanoethyl cellulose and mixtures thereof.
Suitable natural products include, but not limited to, wood, cellulose, lignin-cellulose, paper, cotton, wool, linen, dammars, copols, other natural resins, natural rubber, natural proteins, e.g., soya bean protein, silk, glues gelatin, etc., modified cellulose and mixtures thereof
Any suitable isocyanate may be used in this invention, organic polyisocyanates are preferred. The commercial available ones are preferred such as tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, polymethylene polyphenyl isocyanate, diphenylmethane 4,4xe2x80x2-diisocyanate, 3-methlydiphenyl-methane-4,4xe2x80x2-diisocyanate, m- and p-phenylenediisocyanante, polyphenylpolymethylene isocyanates obtained by phosgenation, commercially known as xe2x80x9ccrude MDIxe2x80x9d, modified polyisacyanates and mixtures thereof. Suitable organic polyisocyanates are exemplified by the organic diisocyanate which are compounds of the general formula
Oxe2x95x90Cxe2x95x90Nxe2x80x94Rxe2x80x94Nxe2x80x94Cxe2x95x90O
wherein R is a divalent organic radical such as an alkylene, aralkylene or arylene radical. Such radical may contain 2 to 20 carbon atoms. Any suitable compound with active hydrogens may be reacted with the polyisocyanates to produce polyurethane products. The preferred compound with active hydrogens are polyols. Polyurethane catalyst, blowing agents, surfactants, foam stabilizers, dyestuff, plasticizers, propellant, desiccant and fillers may also be used. Polyisocyanate which has the formula
Q(NCO)m
in which m represent a number from 2 to 4 and Q represents an aliphatic hydrocarbon radical having 2 to 18 C atoms, a cycloaliphatic hydrocarbon radical having 4 to 15 C atoms, an aromatic hydrocarbon radical having 6 to 15 C atoms, or araliphatic hydrocarbon radical having 8 to 15 C atoms and an organic compounds with 1 or more active hydrogens which will react with an isocyanate, containing a urethane catalyst, a plasticizer, propellants and a silicone surfactant may be used as the flammable organic material. Any suitable polyepoxy compounds may be used in this invention such as ally glycidyl ether, tert-butyl glycidyl ether and other polyepoxides.
Any suitable thermoplastic resin may be used in this invention. Suitable thermoplastic resins include the olefin polymers. The olefin polymers include, for example, homopolymers and copolymers of olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1 and the like and, specific samples thereof include polyethylene, polypropylene, ethylene-polypropylene copolymers, ethylene-butene-I copolymer ethylene-hexene-1 copolymers, and ethylene-octene-1 copolymers.
Said olefin polymers also include copolymers of said olefin with polar monomers comprising the olefin unit as the main constituent, specifically ethylene-vinyl acetate copolymer, ethylene-methymethacrylate copolymer, ethylene-acrylic acid copolymer, ethylene-vinyl alcohol copolymer and the like. These olefin polymers may be used alone or in combination of two or more. The thermoplastic resin in this invention includes homopolymers and copolymers of unsaturated carboxylic acids and their alkyl esters, such as acrylic acid, methacrylic acid, methylacrylate, methylmethacrylate, and the like, and vinyl esters of saturated carboxylic acids such as vinyl acetate, vinyl butrate and the like. These homopolymers and copolymers may be used alone or in combination of two or more.
Said vinyl aromatic polymers include, for example, homopolymer and coploymers of styrene monomers such as styrene, a-methylstyrene and vinyl styrene, and specific examples thereof polystyrene, poly-a-methylstyrenes,polyvinyltoluene, styrene-a-methylstyrene copolymers and the like. The vinyl aromatic polymers further include, for example, copolymers of styrene with acrylonitrile monomer, maleimide monomer, acrylic acid ester monomer, maleic acid monomer, and specific examples include styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-methylacrylate copolymer, styrene-maleic anhydride copolymer and the like.
Said vinyl aromatic polymers may also be modified with a rubbery polymer, and the rubbery polymer includes, for example, polybutadiene, styrene-butadiene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene-diene copolymer,butadiene-acrylic acid ester copolymer and the like. These vinyl aromatic polymers may be used alone or in combination of two or more.
Furthermore, the thermoplastic resin in this invention includes also engineering plastics such as polyphenylene ether, rubber-modified polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, polyacetal, polysulfone, polyethersulfone, polyphenyene sulfide, polyarylate, polyamide-imide, polyetheramide, polyetherketone, polyetheretherketone, polyimide and the like. The thermoplastic resins in this invention may also be chemically modified products, blends and alloyed products of the above-mentioned thermoplastic resins or may be reinforced with glass fiber or the like.
As the thermoplastic resin to be used in this invention, among the above-mentioned examples, particularly preferable in industry are those consisting of one or more olefin polymers mentioned above or those consisting of one or more vinyl aromatic polymers in view of the moldability and mechanical properties of a flame retardant resin composition prepared by mixing the thermoplastic resin with component (2), an organic phosphorus-inorganic phosphorus oxyacid compound or component (3), a salt of an organic phosphorus-inorganic oxyacid compound, component (4), a comb-like polymer, (5) a metal-containing compound having a carbonization accelerating effect, component (6), a carbonization auxiliary, and (7) a filler.
When halogen-containing resins, for example, polyvinyl chloride, polyvinyldiene chloride, chlorinated polyethylene, chlorosulfonated polyethylene and the like, are used as polymer of this invention, the flame retardant can be improved, but the halogen-containing resins become a source of generating a toxic gas due to the halogenelement contained therein when the resins are burned, and hence, are not the optimum resins to be used in this invention.
Component (2), a organic phosphorus-inorganic phosphorus oxyacid compounds which are produced by reaction component A, an organic phosphorus compound containing phosphorus which has a valence of 3 or 4, and component B, an inorganic phosphorus oxyacid compound containing phosphorus which has a valence of 5.
Component (3), salt of organic phosphorus-inorganic phosphorus oxyacids compounds are produced by the process of this invention as stated above, by reacting component A, an organic phosphorus compound and component B, an inorganic phosphorus compound, thereby producing an organic phosphorus-inorganic phosphorus oxyacid compound which is then reacted with component C, a salt forming compound. The preferred salt of an organic phosphorus-inorganic phosphorus oxyacid compounds to be use to flame retard thermoplastic resins are nitrogen containing salts of organic phosphorus-inorganic phosphorus oxyacid compounds. The preferred nitrogen containing compound is biuret or a combination of biuret and another amino compound and/or ammonia compound. The preferred organic phosphorus compounds are or organic phosphonate compounds, for example, phosphonicacid, methyl-,(5-ethyl-2methyl-1,2,3-dioxaphosphorinan-5-yl)methyl,methyl ester, P-oxide and phosphonic acid,ethyl-,bis(5-ethyl-2-methyl-1,2,3-dioxaphosphorinan-5-yl)methyl]ester, P,Pxe2x80x2dioxide.
A comb like polymer consisting of a polyethyene main chain and a polyoxyalkylene main chain and a polyoxyalkylene side chain can be obtained by, for example, graft-copolymerization of a cyclic ether such as ethylene oxide or propylene oxide to a saponification product of an ethylene-vinyl acetate copolymer, esterification between ethylene-vinyl acid copolymer and polyethylene glycol, poly-propylene glycol or the like, copolymerization of ethylene with w-hydroxypolyethylene oxide macromonomer, or the like. As its production process, the disclosed in Japanese Patent Application is practicable which is a production process comprising heating an ethylene-vinyl acetate copolymer and an alcohol in the presence of an alkali catalyst to saponify them, removing the alcohol and then introducing alkylene oxide there into to form a graft copolymer.
A metal-containing compound having carbonization accelerating effect used in this invention increases the amount of carbonization residue after combustion, thereby enhancing the flame retarding effect. These compounds include, but not limited to, alkaline earth metal borates such as magnesium borate, calcium magnesium borate, manganese borate, zinc borate and the like, metal oxides such as titanium oxide, tin oxide, nickel oxide, zinc oxide and the like, ferrocene, dimethylglyoxime copper, acetyl-acetonatocopper, hydroxyquinoline nickel and the like, zinc thiocarbamate compounds such as zinc dimethylthio-carbamate, zinc di-n-butyldithiocarbamate and the like, mercaptobenzothiazole zinc compounds such as mercaptobenzothiazole zinc and the like, salicylaldehyde zinc compounds such as salicylaldehyde zinc and the like, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium magnesium hydroxide, zirconium hydroxide and the like.
The most preferable compounds are selected from zinc oxide, the zinc thiocarbamate compounds, the mercaptobenzothiazole zinc compounds, the salicyaldehyde zinc compounds, zinc borate and the alkaline earth metal borates.
The components are mixed and reacted under conditions sufficient to prepare the organic phosphorus-inorganic phosphorus oxyacid compounds and/or composition and flame retarded organic materials. Many of the reactions will take place at ambient temperature and pressure. Most of the reactions are exotherinc and may require cooling. Some of the reactions may be speeded up by using an elevated temperature of 100xc2x0 to 300xc2x0 C. and pressure. When a gas is used it may be necessary to use increased pressure to compress the gas in order to form a liquid.
It is preferred for the organic phosphorus compound to contain a phosphorus atom which has a valence of 3 so that the phosphorus atom will have 2 remaining valences to react with the inorganic phosphorus oxyacid compound which contain a phosphorus atom which has a valence of 5. The inorganic phosphorus oxyacid had active hydrogens to react with the 2 free valences of the organic phosphorus compound. The organophosphorus compounds with a coordination number of four (xe2x80x9cpentavalentxe2x80x9d phosphorus compounds) such as esters of phosphonic acid will also react with inorganic phosphorus oxyacid compounds. The organic phosphates has an active oxygen on the phosphorus atom which will react with the inorganic phosphorus oxyacid compounds. The organic phosphorus-inorganic phosphorus oxyacid compounds may be produced as a neutral, mildly acidic or moderate acidic compounds. Phosphoric acid will react with organic phosphonates to form compounds such as:
1) equals mols of organic phosphonate and phosphoric acid are reacted to produce 
2) two mols of organic phosphonate are reacted with one mol of phosphoric acid to produce 
3) One mol of organic phosphonate is reacted with two mols of phosphoric acid to produce 
Organic phosphites will react with phosphoric acid to produce organic phosphorus-inorganic phosphorus oxyacids such as:
1) equal mols of an organic phosphite is reacted with phosphoric acid thereby producing: 
2) two mols of an organic phosphite are reacted with one mol of phosphoric acid thereby producing: 
3) two mols of phosphoric acid are reacted with one mol of organic phosphite thereby producing: 
Organic phosphates will react with phosphoric acid to produce organic phosphorus-inorganic phosphorus oxyacid compounds such as:
1) equal mols of an organic phosphate and phosphoric acid are reacted to produce; 
2) two mols of an organic phosphate and one mol of phosphoric acid are reacted to produce; 
Organic esters of acids of trivalent phosphorus or phosphorus with a coordination valence of four will react with phosphoric acid to produce organic phoshorus-phosphorus oxyacids compounds such as:
1) equal mols of a phosphonic ester and phosphoric acid are reacted to produce organic phosphorus-phosphorus oxyacid compounds such as 
2) two mols of a phosphonic ester and one mol of phosphoric acid are reacted to produce organic phosphorus-phosphorus oxyacid compounds such as; 
3) two mols of phosphoric acid and one mol of phosphonic ester are reacted to produce organic phosphorus-phosphorus oxyacid compounds such as; 
Wherein R is an alkyl, aryl , alkyl-aryl, cyclic, dialkyl alkyl, hydrogen or other organic radicals or mixture thereof.
The salt of organic phosphorus-inorganic phosphorus oxyacid compounds are usually produced by mixing and reacting the organic phosphorus compound with the inorganic phosphorus oxyacid compound to produce an organic phosphorus-inorganic phosphorus oxyacid compound, and then the basic salt forming compound is added and reacted thereby producing a salt of organic phosphorus-inorganic phosphorus oxyacid compound. These reactions are usually exothermic but in some reactions it is necessary to heat the mixture up to 300xc2x0 C. Then the comb-like polymer, carbonization auxiliaries, carbonization accelerators and fillers are added and mixed with the salt of organic phosphorus-inorganic phosphorus oxyacid compound to form a flame retardant composition. The flame retardant salt of organic phosphorus-inorganic oxyacid compound and/or the flame retardant composition is added on or mixed in the more flammable organic material.
In this invention, the method of mixing the thermoplastic resin, the organic phosphorus-inorganic phosphorus oxyacid compound, salt of organic phosphorus-inorganic phosphorus oxyacid compound and/or composition, comb-like polymer consisting of a polyethylene main chain and a polyoxyalkylene side chain and a metal-containing compound having a carbonization accelerating effect is not critical. All the above components, thermoplastic resin, organic phosphorus-inorganic phosphorus oxyacid compound and/or composition, salt of organic inorganic phosphorus-inorganic phosphorus oxyacid and/or composition, comb-like polymer, carbonization auxiliaries and metal containing compound may added simultaneously then mixed together by any suitable means. They may be mixed together by using a Banbury mixer, an open roller, a kneader, a single or multiple screw extruder or the like with or without or after mixing by a Henschel mixer, a tumbler mixer or the like. The said mixture is heated until the thermoplastic resin softens or melts, then is thoroughly mixed, then extruded or molded into a desired shape. The organic phosphorus-inorganic phosphorus oxyacid compound and basic salt forming compound may be may be added separate with the thermoplastic resin, and are reacted when the mixture is heated.
The flame retardant thermoplastic composition of this invention may if necessary, have added thereto a heat stabilizer, an antioxidant, a light stabilizer, a lubricant, an antifogging agent, a pigment, a blowing agent, a fluorescent agent, a release agent, a processing aid, a reinforcing agent, and the like which are generally added to a thermoplastic resin, depending upon the uses of the composition. A known flame-retardant such as a halogen-containing flame retardant, an inorganic flame retardant or the like may also be added to the thermoplastic resin.
The following examples which describe certain preferred embodiment of the processes may, of course, be varied as described above with similar results. This invention is not limited to the examples below. Parts and percentages are by weight unless otherwise indicated.
The following Reference Examples shows method for producing the organic phosphorus-inorganic phosphorus oxyacid compounds and composition, basic salt of organic phosphorus-inorganic phosphorus oxyacid compounds and compositions, and the comb-like polymer consisting of a polyethylene main chain and a polyoxyalkylene side chain.